CN105348254A - Method for preparing 1,3-propane sultone - Google Patents
Method for preparing 1,3-propane sultone Download PDFInfo
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- CN105348254A CN105348254A CN201510907189.7A CN201510907189A CN105348254A CN 105348254 A CN105348254 A CN 105348254A CN 201510907189 A CN201510907189 A CN 201510907189A CN 105348254 A CN105348254 A CN 105348254A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
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Abstract
The invention discloses a method for preparing 1,3-propane sultone. The method includes the steps that (1) 1,3-propanesulfonic acid is prepared: sodium sulfite, sodium bisulfite and allyl alcohol are added into a reactor under the room temperature condition, a pH value is regulated to be 5 to 5.5, infrared radiation induction is adopted, azo diisobutyl nitrile performs catalytic reaction for 2 to 3 hours, concentrated hydrochloric acid is added, the reaction is performed at the temperature of 85 to 90 DEG C for 2 to 3 hours, generated salt is removed through filtration, and n-butyl alcohol is added into filtrate to perform extraction separation so as to obtain the 3-hydroxy-1-propanesulfonic acid; (2) the 1,3-propane sultone is prepared: pyridinium p-toluenesulfonate and zeolites are added, dehydration reaction is performed at the temperature of 50-60 DEG C for 2-3 hours, distillation is performed to obtain 147-149 DEG C of fraction, and calcium oxide is added to perform heating reflux for 1-2 hours to obtain the 1,3-propane sultone. The product prepared by means of the method is high in yield and purity. In addition, the moisture content of the product is mostly above 0.1%, the amplification effect and other problems do not exist, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method, be specifically related to a kind of method of PS.Belong to chemosynthesis technical field.
Background technology
1,3-N-morpholinopropanesulfonic acid lactone is a kind of colourless or light yellow transparent liquid (more than 31 DEG C) or water white transparency crystallization (less than 31 DEG C), industrially to be mainly used in: sulphonating agent, for process hides, ink and sensitizing dye synthesis, the synthesis starting raw material of electroplating intermediate, medicine intermediate, tensio-active agent, lithium secondary battery etc.Along with its purposes is more and more extensive, market demand is also increase year by year.But, current 1, the problems such as the synthetic method ubiquity temperature of reaction height of 3-N-morpholinopropanesulfonic acid lactone, cause that product yield is low, purity is not high yet, in addition, product water content major part is higher than 0.1%, can not be applicable to require meticulous Application Areas, existing preparation technology also only can meet laboratory short run preparation, there is the problems such as scale effect, is not suitable for suitability for industrialized production.
Summary of the invention
The object of the invention is, for overcoming above-mentioned the deficiencies in the prior art, to provide a kind of method preparing PS.
For achieving the above object, the present invention adopts following technical proposals:
Prepare a method for PS, comprise step:
(1) 1, the preparation of 3-N-morpholinopropanesulfonic acid: under room temperature condition, in reactor, add S-WAT, sodium bisulfite and vinylcarbinol, pH value is adjusted to 5 ~ 5.5, and infrared ray radiation is induced, azo diisobutyl nitrile catalyzed reaction 2 ~ 3 hours, add concentrated hydrochloric acid, 85 ~ 90 DEG C are reacted 2 ~ 3 hours, cross the salt filtering generation, filtrate adds n-butanol extraction and is separated, and obtains 3-hydroxyl-1-propanesulfonic acid; Wherein, the ratio of the amount of substance of vinylcarbinol, S-WAT, sodium bisulfite is 1: 1.0 ~ 1.05: 0.1 ~ 0.2, and the mass volume ratio of S-WAT, azo diisobutyl nitrile and concentrated hydrochloric acid is 1g.0.1 ~ 0.2g.8 ~ 12mL;
(2) preparation of PS: add pyridinium p-toluenesulfonate and zeolite, 50 ~ 60 DEG C are carried out dehydration reaction 2 ~ 3 hours, rectifying, get 147 ~ 149 DEG C of cuts, add calcium oxide reflux 1 ~ 2 hour, to obtain final product; The mass ratio of 3-hydroxyl-1-propanesulfonic acid, pyridinium p-toluenesulfonate, zeolite and calcium oxide is 10 ~ 12: 0.1 ~ 0.2: 0.2 ~ 0.3: 0.1 ~ 0.2.
Described room temperature is 25 ~ 30 DEG C.
Preferably, in described step (1), concentrated hydrochloric acid adjust ph is utilized.
Preferably, in described step (1), azo diisobutyl nitrile catalyzed reaction 2 ~ 2.5 hours.
Preferably, in described step (1), the ratio of the amount of substance of vinylcarbinol, S-WAT, sodium bisulfite is 1: 1.0: 0.2.
Preferably, in described step (1), the mass volume ratio of S-WAT, azo diisobutyl nitrile and concentrated hydrochloric acid is 1g: 0.1g: 12mL.
Preferably, in described step (2), 55 DEG C are carried out dehydration reaction 2.5 hours.
Preferably, in described step (2), the mass ratio of 3-hydroxyl-1-propanesulfonic acid, pyridinium p-toluenesulfonate, zeolite and calcium oxide is 11: 0.15: 0.3: 0.1.
Beneficial effect of the present invention:
The present invention prepares 1 at one kettle way, 3-N-morpholinopropanesulfonic acid, eliminates 1, the purification process of 3-N-morpholinopropanesulfonic acid sodium, pH being controlled 5 ~ 5.5, in conjunction with utilizing the catalysis of azo diisobutyl nitrile, 1 can be obtained by reacting at ambient temperature, 3-N-morpholinopropanesulfonic acid sodium, without purification, utilize concentrated hydrochloric acid to carry out acidifying further and prepare 1,3-N-morpholinopropanesulfonic acid, and vinylcarbinol almost 100% is converted into 3-hydroxyl-1-propanesulfonic acid; 1,3-N-morpholinopropanesulfonic acid and then Dehydration obtain 1,3-N-morpholinopropanesulfonic acid lactone, introduce the combination catalyst of pyridinium p-toluenesulfonate and zeolite, the temperature of effective reduction dehydration reaction, and add calcium oxide and dewater, effectively reduce water content, by water content control below 0.02%, be specially adapted to require meticulous Application Areas.
Product yield of the present invention is high, and purity is high, and in addition, product water content major part higher than 0.1%, and does not exist the problems such as scale effect, is applicable to suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention will be further elaborated, should be noted that following explanation is only to explain the present invention, not limiting its content.
Embodiment 1:
Prepare a method for PS, comprise step:
(1) 1, the preparation of 3-N-morpholinopropanesulfonic acid: under room temperature condition, in reactor, add 126g S-WAT, 104g sodium bisulfite and 5.8g vinylcarbinol, concentrated hydrochloric acid adjust ph is 5, and infrared ray radiation is induced, 12.6g azo diisobutyl nitrile catalyzed reaction 2 hours, add 1008mL concentrated hydrochloric acid, 85 DEG C are reacted 2 hours, cross the salt filtering generation, filtrate adds n-butanol extraction and is separated, and obtains 14g3-hydroxyl-1-propanesulfonic acid;
(2) 1, the preparation of 3-N-morpholinopropanesulfonic acid lactone: get 10g3-hydroxyl-1-propanesulfonic acid, add 0.1g pyridinium p-toluenesulfonate and 0.2g zeolite, 50 DEG C are carried out dehydration reaction 2 hours, rectifying, gets 147 ~ 149 DEG C of cuts, adds 0.1g calcium oxide reflux 1 ~ 2 hour, obtain PS 8.7g.Total recovery is 99%, and purity is more than 99.99%, and water content is less than 0.02%.
Embodiment 2:
Prepare a method for PS, comprise step:
(1) 1, the preparation of 3-N-morpholinopropanesulfonic acid: under room temperature condition, 126g S-WAT, 109.2g sodium bisulfite and 11.6g vinylcarbinol is added in reactor, concentrated hydrochloric acid adjust ph is 5.5, and infrared ray radiation induction 25.2g azo diisobutyl nitrile catalyzed reaction 3 hours, adds 1512mL concentrated hydrochloric acid, 90 DEG C are reacted 3 hours, cross the salt filtering generation, filtrate adds n-butanol extraction and is separated, and obtains 28g3-hydroxyl-1-propanesulfonic acid;
(2) 1, the preparation of 3-N-morpholinopropanesulfonic acid lactone: get 12g3-hydroxyl-1-propanesulfonic acid, add 0.2g pyridinium p-toluenesulfonate and 0.3g zeolite, 60 DEG C are carried out dehydration reaction 3 hours, rectifying, gets 147 ~ 149 DEG C of cuts, adds 0.2g calcium oxide reflux 1 ~ 2 hour, obtain PS 10.38g.Total recovery is 99.3%, and purity is more than 99.99%, and water content is less than 0.02%.
Embodiment 3:
Prepare a method for PS, comprise step:
(1) 1, the preparation of 3-N-morpholinopropanesulfonic acid: under room temperature condition, in reactor, add 126g S-WAT, 104g sodium bisulfite and 11.6g vinylcarbinol, concentrated hydrochloric acid adjust ph is 5.5, and infrared ray radiation is induced, 12.6g azo diisobutyl nitrile catalyzed reaction 2.5 hours, add 1512mL concentrated hydrochloric acid, 90 DEG C are reacted 2 hours, cross the salt filtering generation, filtrate adds n-butanol extraction and is separated, and obtains 28g3-hydroxyl-1-propanesulfonic acid;
(2) 1, the preparation of 3-N-morpholinopropanesulfonic acid lactone: get 11g3-hydroxyl-1-propanesulfonic acid, add 0.15g pyridinium p-toluenesulfonate and 0.3g zeolite, 55 DEG C are carried out dehydration reaction 2.5 hours, rectifying, gets 147 ~ 149 DEG C of cuts, adds 0.1g calcium oxide reflux 2 hours, obtain PS 9.53g.Total recovery is 99.4%, and purity is more than 99.99%, and water content is less than 0.02%.
Embodiment 4:
Prepare a method for PS, comprise step:
(1) 1, the preparation of 3-N-morpholinopropanesulfonic acid: under room temperature condition, in reactor, add 12.6kg S-WAT, 10.4kg sodium bisulfite and 1.16kg vinylcarbinol, concentrated hydrochloric acid adjust ph is 5.5, and infrared ray radiation is induced, 1.26kg azo diisobutyl nitrile catalyzed reaction 2.5 hours, add 151.2L concentrated hydrochloric acid, 90 DEG C are reacted 2 hours, cross the salt filtering generation, filtrate adds n-butanol extraction and is separated, and obtains 2.8kg3-hydroxyl-1-propanesulfonic acid;
(2) 1, the preparation of 3-N-morpholinopropanesulfonic acid lactone: get 1.1kg3-hydroxyl-1-propanesulfonic acid, add 0.015kg pyridinium p-toluenesulfonate and 0.03kg zeolite, 55 DEG C are carried out dehydration reaction 2.5 hours, rectifying, gets 147 ~ 149 DEG C of cuts, adds 0.01kg calcium oxide reflux 2 hours, obtain PS 0.953kg.Total recovery is 99.4%, and purity is more than 99.99%, and water content is less than 0.02%.
Embodiment 5:
Prepare a method for PS, comprise step:
(1) 1, the preparation of 3-N-morpholinopropanesulfonic acid: under room temperature condition, in reactor, add 126kg S-WAT, 104kg sodium bisulfite and 116kg vinylcarbinol, concentrated hydrochloric acid adjust ph is 5.5, and infrared ray radiation is induced, 12.6kg azo diisobutyl nitrile catalyzed reaction 2.5 hours, add 1512L concentrated hydrochloric acid, 90 DEG C are reacted 2 hours, cross the salt filtering generation, filtrate adds n-butanol extraction and is separated, and obtains 28kg3-hydroxyl-1-propanesulfonic acid;
(2) 1, the preparation of 3-N-morpholinopropanesulfonic acid lactone: get 11kg3-hydroxyl-1-propanesulfonic acid, add 0.15kg pyridinium p-toluenesulfonate and 0.3kg zeolite, 55 DEG C are carried out dehydration reaction 2.5 hours, rectifying, gets 147 ~ 149 DEG C of cuts, adds 0.1kg calcium oxide reflux 2 hours, obtain PS 9.53kg.Total recovery is 99.4%, and purity is more than 99.99%, and water content is less than 0.02%.
Embodiment 6:
Prepare a method for PS, comprise step:
(1) 1, the preparation of 3-N-morpholinopropanesulfonic acid: under room temperature condition, in reactor, add 1260kg S-WAT, 1040kg sodium bisulfite and 1160kg vinylcarbinol, concentrated hydrochloric acid adjust ph is 5.5, and infrared ray radiation is induced, 126kg azo diisobutyl nitrile catalyzed reaction 2.5 hours, add 15120L concentrated hydrochloric acid, 90 DEG C are reacted 2 hours, cross the salt filtering generation, filtrate adds n-butanol extraction and is separated, and obtains 280kg3-hydroxyl-1-propanesulfonic acid;
(2) 1, the preparation of 3-N-morpholinopropanesulfonic acid lactone: get 110kg3-hydroxyl-1-propanesulfonic acid, add 1.5kg pyridinium p-toluenesulfonate and 3kg zeolite, 55 DEG C are carried out dehydration reaction 2.5 hours, rectifying, gets 147 ~ 149 DEG C of cuts, adds 1kg calcium oxide reflux 2 hours, obtain PS 95.3kg.Total recovery is 99.4%, and purity is more than 99.99%, and water content is less than 0.02%.
Although above-mentioned, the specific embodiment of the present invention is described; but not limiting the scope of the invention; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (7)
1. prepare a method for PS, it is characterized in that, comprise step:
(1) 1, the preparation of 3-N-morpholinopropanesulfonic acid: under room temperature condition, in reactor, add S-WAT, sodium bisulfite and vinylcarbinol, pH value is adjusted to 5 ~ 5.5, and infrared ray radiation is induced, azo diisobutyl nitrile catalyzed reaction 2 ~ 3 hours, add concentrated hydrochloric acid, 85 ~ 90 DEG C are reacted 2 ~ 3 hours, cross the salt filtering generation, filtrate adds n-butanol extraction and is separated, and obtains 3-hydroxyl-1-propanesulfonic acid; Wherein, the ratio of the amount of substance of vinylcarbinol, S-WAT, sodium bisulfite is 1: 1.0 ~ 1.05: 0.1 ~ 0.2, and the mass volume ratio of S-WAT, azo diisobutyl nitrile and concentrated hydrochloric acid is 1g: 0.1 ~ 0.2g: 8 ~ 12mL;
(2) preparation of PS: add pyridinium p-toluenesulfonate and zeolite, 50 ~ 60 DEG C are carried out dehydration reaction 2 ~ 3 hours, rectifying, get 147 ~ 149 DEG C of cuts, add calcium oxide reflux 1 ~ 2 hour, to obtain final product; The mass ratio of 3-hydroxyl-1-propanesulfonic acid, pyridinium p-toluenesulfonate, zeolite and calcium oxide is 10 ~ 12: 0.1 ~ 0.2: 0.2 ~ 0.3: 0.1 ~ 0.2.
2. a kind of method preparing PS according to claim 1, is characterized in that, in described step (1), utilizes concentrated hydrochloric acid adjust ph.
3. a kind of method preparing PS according to claim 1, is characterized in that, in described step (1), and azo diisobutyl nitrile catalyzed reaction 2 ~ 2.5 hours.
4. a kind of method preparing PS according to claim 1, is characterized in that, in described step (1), the ratio of the amount of substance of vinylcarbinol, S-WAT, sodium bisulfite is 1: 1.0: 0.2.
5. a kind of method preparing PS according to claim 1, is characterized in that, in described step (1), the mass volume ratio of S-WAT, azo diisobutyl nitrile and concentrated hydrochloric acid is 1g: 0.1g: 12mL.
6. a kind of method preparing PS according to claim 1, is characterized in that, in described step (2), 55 DEG C are carried out dehydration reaction 2.5 hours.
7. one according to claim 1 prepares 1, the method of 3-N-morpholinopropanesulfonic acid lactone, it is characterized in that, in described step (2), the mass ratio of 3-hydroxyl-1-propanesulfonic acid, pyridinium p-toluenesulfonate, zeolite and calcium oxide is 11: 0.15: 0.3: 0.1.
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| CN201510907189.7A CN105348254A (en) | 2015-12-11 | 2015-12-11 | Method for preparing 1,3-propane sultone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397392A (en) * | 2016-08-31 | 2017-02-15 | 湖北吉和昌化工科技有限公司 | 1,4-butane sultone and synthesis process thereof |
| CN112321561A (en) * | 2020-09-28 | 2021-02-05 | 常熟聚和化学有限公司 | Method for preparing 1, 3-propane sultone from 3-hydroxypropanesulfonic acid |
| CN115677651A (en) * | 2022-12-08 | 2023-02-03 | 青岛科技大学 | Preparation method of alkyl sultone |
-
2015
- 2015-12-11 CN CN201510907189.7A patent/CN105348254A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 张敏等: ""新型电镀光亮剂吡啶丙烷磺酸内盐的合成"", 《江苏化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397392A (en) * | 2016-08-31 | 2017-02-15 | 湖北吉和昌化工科技有限公司 | 1,4-butane sultone and synthesis process thereof |
| CN112321561A (en) * | 2020-09-28 | 2021-02-05 | 常熟聚和化学有限公司 | Method for preparing 1, 3-propane sultone from 3-hydroxypropanesulfonic acid |
| CN112321561B (en) * | 2020-09-28 | 2022-04-08 | 常熟聚和化学有限公司 | Method for preparing 1, 3-propane sultone from 3-hydroxypropanesulfonic acid |
| CN115677651A (en) * | 2022-12-08 | 2023-02-03 | 青岛科技大学 | Preparation method of alkyl sultone |
| CN115677651B (en) * | 2022-12-08 | 2023-11-14 | 青岛科技大学 | Preparation method of alkyl sultone |
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Application publication date: 20160224 |